Colored cleaning agents



United States Patent 3,058,916 COLORED CLEANING AGENTS Herbert Sinner, Dusseldorf-Benrath, and Walter Fries, Dusseldorf Unterbach, Germany, assignors to Henkel & Cie. G.m.b.H., Dusseldorf-Holthausen, Germany, a German corporation No Drawing. Filed June 19, 1957, Ser. No. 666,751 Claims priority, application Germany June 28, 1956 2 Claims. (Cl. 252-99) This invention relates to new and useful improvements in colored cleaning agents.

Cleaning agents such as general household detergents, laundry detergents, washing aids, scouring powders and the like which are colored have caught the fancy of housewives and have increasing sales appeal. The coloring as contrasted to the bluing which was used in laundering a number of years ago and the optical dyes which are presently used is not intended to take part in the washing operation, and is merely intended to aid in the physical appearance of the product itself for marketing and sales purposes. The old bluing was used in order to compensate by additive color mixing, for any yellow tinge which laundered articles might still have. In the same manner, modern optical dyes add a light blue tinge to the laundering making the same appear lighter compensating for any yellowing.

Where the coloring agent or dye conventionally added to the cleansing agent in order to color the same is not intended to take part in the cleansing operation, and in connection with textiles would not dye the fibres of the goods to be washed and was not suitable from the standpoint of dyeing technique as a dyestulf for textiles, the same would nevertheless leave a certain slight undesirable color on the goods.

One object in this invention is a cleaning agent which is colored by dye material and which does not have the above mentioned disadvantage of even slightly coloring the goods washed therewith. This and still further objects will become apparent from the following description:

In accordance with the invention it has been found that the above mentioned disadvantages may be avoided by using a dyestuff, thecolor of which is at least substantially destroyed by oxidation in combination with a cleaning agent containing'amoxid izipgjiiaterial, in order to color the cleaning agent. i

The cleaning agents which may be used in accordance with the invention include any of the known or conventional cleaning agent such as the detergents, washing aids or scouring powders. The term detergents as used herein is intended to designate any of the agents conventionally used for removing soil, such as general household detergents or laundry detergents of the synthetic or soap type. These agents generally contain about 10 to 60% by weight of materials which are actually active in remov ing the soil.

The term washing aids as used herein is intended to designate conventional softening steeping, prewashing or rinsing agents having a smaller content of materials which actively aid in removing the soil as for example from 0 to 5% by weight thereof.

The term scouring powders as used herein is intended to designate conventional cleansing powders or agents used in connection with cleaning porcelain and enamel surfaces, cooking utensils and the like which contain in addition to soil removing detergents insoluble abrasive powders.

The oxidizing agents which destroy the color of the dye in accordance with the invention are preferably oxidizing agents which are conventionally present in the cleaning agents as for example, compounds which contain active oxygen such as inorganic or organic percompounds.

The inorganic per-compounds include perborates, percarbonates, perphosphates, perpyrophosphates, and the well known molecular compounds of hydrogen peroxide and urea. As organic per-compounds, there may be mentioned in particular percarboxylic acids and their salts, diacylperoxides and percarboxylates. The organic per-compounds can be derived from aliphatic or aromatic carboxylic acids having preferably 3 to 26 carbon atoms in the molecule. Such carboxylic acids are for instance the soap-forming fatty acids, aliphatic dicarboxylic acids having 3 to 13 carbon atoms in the molecule and aromatic monoto hexacarboxylic acids having 7 to 26 carbon atoms in the molecule. The active oxygen content of these wasing agents is generally 0.4 to 3 percent by weight.

Otherwise, the cleaning agents such as the detergent composition or washing aid may have any desired composition. The composition of these products should mostly lie within the following formula:

0.5 to 50% by weight wash-active substances 0 to 40% by weight wash-alkali 0 to 30% by weight neutral salt 0 to 50% by weight complex formers 4 to 30% by weight per-compounds 0 to 10% by weight other washing agent components By wash-active substances there are understood the known, hardness resistant or non-hardness resistant substances customarily used for this purpose, such as soaps, alkyl aryl sulfonates, particularly alkylbenzene sulfonates, alkyl or cycloalkylsulfonates, as obtained for instance from aliphatic or cycloaliphatic hydrocarbons by reaction with a mixture of sulfur dioxide and chlorine or sulfur dioxide and oxygen and treatment of the reaction product with caustic alkali solution, as well as fatty alcohol sulfates, fatty acid monoglyceride sulfates, surface-active reaction products of ethylene oxide with fatty alcohols and fatty acids or their partial ethers or partial esters with multivalent alcohols. Furthermore, however, other anion active synthetic surfactants of the sulfate or sulfonate type or non-ionic surfactants can also be used.

The wash alkalis include in particular soda, dior trialkali orthophosphates, alkali borates and alkali silicates. In the case of the latter, the ratio of Na O:SiO can vary within the range 1:1 to 1:4. As neutral salts, there may be present in the detergents or washing aids in particular sodium sulfate and magnesium sulfate, the latter of course only if the washing agents do not contain any surface-active substances which are sensitive to hardness. As complex formers there may be mentioned first of all the anhydric phosphates such as pyro-, metaand polyphosphates or in their stead organic complex formers, particularly ethylene diamino-tetraacetic acid or nitrilotriacetic acid as well as other aminopolycarboxylic acids which contain more carboxyl groups than amine nitrogen atoms in the molecule.

Among the other components there belong in particular stabilizers for the per-compounds such as for instance water-insoluble silicates of bivalent and trivalent metals, particularly magnesium or aluminum, starch or cellulose glycolates, amides, particularly alkylolanndes of fatty acids, alkylbenzenesulfonic acids or alkylsulfonic acids, etc.

To the last groups of washing agent components there also belong the oxidation-sensitive dyestuffs to be used in accordance with the invention, the quantity of which in general is very small, but which depending on the intensity of the color of the dyestuif and the desired shade of the washing agent can vary within wide limits, for instance between 0.001 and 2% by weight of the washing agent. The quantity of dyestufi is generally within the range of 0.01 to 0.1 weight percent so that a washing agent having a soft, pastel-like shade is obtained. The color itself may be any color desired, for instance red, orange, yellow, green, blue or violet.

In order to test the suitability of a dyestuif, a washing agent having the desired shade is prepared. It is dissolved in water and brought to the prescribed temperature of use in the concentration of use of the washing agent, in which connection there are furthermore main tained the periods of time prescribed for the washing process in question. In the case of boil washing agents, the washing liquor for instance is heated for 30 minutes to the boiling point and the liquor is allowed to boil for 10 minutes. If the color of the liquor has disappeared after this treatment, the dyestuff can be used for the purpose of the invention. In addition to the dyestuffs which are completely d'ecolored in the customary use of the washing agent, there can be also used those in which a substantial decoloration takes place. The decoloration should then amount to at least 50% and prefeably 75% in connection with the customay use of the washing agent. The numerical determination of these values must of course be effected colorimetrically by measuring the extinction within the region of the maximum light absorption. Since in colorimetric measurements clouds of the solution, such as are frequently present in washing-agent solutions, are disturbing, clouds must be removed by filtration, centrifuging or other methods. If this is not possible, the test should be effected with model substances, i.e., with mixtures of substances which contain all washing-agent components, with the exception of those which interfere with the colorimetric measurement. These includes also the water-insoluble silicates of bivalent or trivalent metals which act as stabilizers for per-compounds. Since the absence of the stabilizers can effect the oxidizability of the per-compounds, it is necessary to effect the heating of the washing-agent solution in quartz vessels and to work with a distilled water which is free of traces of heavy metals, i.e., which has preferably been distilled several times in quartz apparatus.

The following examples are given by way of illustration and not limition:

Example I A washing agent having the composition 33% by weight fatty acid in the form of sodium soap 15% by weight calcined soda 10% by weight sodium pyrophosphate 15% by weight sodium tripolyphosphate 4% by weight water glass 5% by weight magnesium silicate 0.05% by weight optical dye Balance water is prepared in the customary form by spray drying. There is added to the pasty batch before spraying sufiicient naphthol green B having theo verall formula that the powder contains 0.02% by weight thereof. 92 parts by weight of this green powder are mixed in the known manner with 8 parts by weight of sodium perborate.

If a washing solution is produced with this product with a concentration for use of 10 grams per liter, the green dyestufi which had colored the liquor is destroyed after boiling for 30 minutes. The clothes washed therewith show no traces of the color initially present.

Example 2 A self-acting washing agent having the composition 10% by weight fatty alcohol sulfate (C -C 10% by weight alkyl benzene sulfonate-(alkyl=C -C 2% by weight coconut fatty acid monoethanolamide 40% by weight sodium tripolyphosphate 3% by weight waterglass 0.1% by weight optical dye 0.01% by weight indigo disulfonate 12% by weight perborate Balance water prepared as in Example 1 has a pleasant blue color. If the product is dissolved in a quantity of 6 grams per liter in water, the color is also imparted to the washing liquor. If the liquor is used in a washing machine of the agitator-blade type after a time of heating of 45 minutes with a bath ratio of 1:15 for the washing of dirty clothes, the dye has completely disappeared after washing for 10 minutes at 80 C. The clothing furthermore is not colored.

Example 3 A product consisting of 5% by weight of a surface-active fatty alcohol polyglycol ether 45% by weight of soda 3% by weight sodium pyrophosphate 7% by weight waterglass 3% by weight magnesium silicate 0.15% by weight optical dye 0.02% by weight indigo tetrasulfonate 15% by weight sodium phthalomonoperate Balance water is a blue-colored washing agent which can advantageously be used in drum washing machines, in amount of about 5 to 6 grams per liter of water in a bath ratio 1:5- 1:7. The blue color of the washing agent disappears after washing at a temperature of about 80 C. for about 5 minutes.

Example 4 By the method described in Example 1, a washing agent having the following composition is prepared:

' This washing agent, due to the dye contained in it, has

an attractive blue color. It is dissolved in water in a concentration of 6 grams per liter, and the wash water also assumes a blue color. Dirty clothes are then added to this solution in accordance with a bath ratio 1:10 and heated to the boiling point within 45 minutes. After about 10 minutes at the boiling point, the color completely disappears and the clothes are not colored.

Example 5 Example 4 is repeated using as the dye a dye produced by the same supplier designated Basolan Blue FG Type 8071 A. There is also obtained a blue washing agent which difiers from the one described in Example 4 only by the shade of blue. It can be used in the same manner as the washing agent described in Example 4, and in this case also the blue color disappears upon heating the washing liquor, without the clothes becoming colored.

5 Example 6 The invention can also be employed in connection with scouring powders or agents which consist of a waterinsoluble abrasive-acting scouring agent and a water-soluble dirt-loosening component, the water-insoluble component being generally present in excess. Such a scouring agent has for instance the following composition:

79.09% by weight finely ground quartz flour 8% by weight Na P O 3% by weight alkylbenzene sulfonate (sodium salt, alkyl radical =Cm-Cm) 2% by weight NaBO -H O -3H O 0.01% by weight indigo disulfonate In order to prepare such a product, one may for instance convert a pasty batch of all water-soluble components with the exception of the perborate and possibly with the exception of the dye in the known manner by hot atomization into a fine powder. If this powder does not yet contain a blue dye, it is then colored blue by spraying with an aqueous alcoholic solution (1:1) of the dyestufi. Thereupon perborate and quartz flour are admixed and the final blue-colored scouring agent is obtained.

If this scouring agent is applied in the known manner in the presence of water, for instance by a moist rag, the scouring agent retains its original color for a short time, then however progressively losing it due to the action of the perborate. After about 5 minutes, the dyestuff is entirely bleached so that no discoloration of the scoured object can occur as a result of the depositing of the dye in grooves or pores. The decolorization of the slurry takes place even more rapidly if lukewarm water is used for the scouring. Instead of the composition described 6 in the Examples 1-6 there may be used those washing or scouring powders wherein the synthetic capillary active substance is partly or completely replaced by soap.

The invention is preferably directed to agents in pourable form for instance in the form of fine or granular powders.

We claim:

1. A laundry detergent in solid form decoratively colored by a dye capable of being oxidized to a substantially colorless form and additionally containing an oxygenyielding material present in amount sufiicient to substantially oxidize said dye to colorless form in an aqueous washing solution of said laundry detergent.

2. A laundry detergent according to claim 1 in which said dye is a member selected from the group consisting of naphthol green B, indigo disulfonate, and indigo tetrasulfonate, and in which said oxygen yielding material is sodium perborate.

References Cited in the file of this patent UNITED STATES PATENTS 166,609 Hoge et a1. Aug. 10, 1875 18 1,522,846 Tseng Jan. 13, 1925 1,555,588 Korselt Sept. 29, 1925 9; 2,162,255 Heald June 13, 1939 "M 2,498,343 Rider et al. Feb. 21, 1950 We f 2,502,88l Parker Apr. 4, 1950- 1" 2,706,178 Young Apr. 12, 1955 2,739,130 Combs Mar. 20, 1956 2,809,937 Gray Oct. 15, 1957- 44, A

OTHER REFERENCES Modern Soap and Detergent Industry," Martin vol. 11, sec. 1, (1951) pp. l8, 19, 23 and 58, pub. by Technical Press Ltd., London. 

1. A LAUNDRY DETERGENT IN SOLID FORM DECORATIVELY COLORED BY A DYE CAPABLE OF BEING OXIDIZED TO SUBSTANTIALLY COLORLESS FORM AND ADDITIONALLY CONTAINING AN OXYGENYIELDING MATERIAL PRESENT IN AMOUNT SUFFICIENT TO SUBSTANTIALLY OXIDIZE SAID DYE TO COLORLESS FORM IN AN AQUEOUS WASHING SOLUTION OF SAID LAUNDRY DETERGENT 